CN113066973A - Self-supporting vanadium graphene interface zinc storage material and preparation method and application thereof - Google Patents
Self-supporting vanadium graphene interface zinc storage material and preparation method and application thereof Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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Abstract
The invention provides a self-supporting vanadium graphene interface zinc storage material and a preparation method and application thereof, and relates to the technical field of nano materials and electrochemistry, wherein the preparation method comprises the following steps: mixing graphene, vanadium sol and n-propanol, obtaining a vanadium dioxide graphene composite material by adopting a hydrothermal synthesis method, uniformly mixing the vanadium dioxide graphene composite material with a carbon nano tube, crushing, and performing suction filtration to obtain the self-supporting vanadium graphene interface zinc storage material. According to the preparation method, a hydrothermal method is combined with suction filtration, vanadium dioxide sub-nanoclusters and graphene are compounded, the vanadium dioxide sub-nanoclusters and the graphene surface form chemical bond connection, and a self-supporting vanadium graphene interface zinc storage material capable of being embedded into a zinc ion heterogeneous interface in a reversible mode is formed; the prepared self-supporting vanadium graphene interface zinc storage material is used as a zinc ion battery anode active material, and has the advantages of good electrochemical performance, excellent rate capability, high specific capacity and high cycle stability.
Description
Technical Field
The invention relates to the technical field of nano materials and electrochemistry, in particular to a self-supporting vanadium graphene interface zinc storage material and a preparation method and application thereof.
Background
Compared with the organic electrolyte commonly used by the lithium ion battery, the aqueous electrolyte has the advantages of higher ionic conductivity, higher safety, lower production cost and the like. The zinc has the characteristics of large storage capacity, no toxicity and the like, and shows good stability and high theoretical capacity (820 mAh.g) in the aqueous electrolyte-1) And Zn/Zn2+Has a lower oxidation-reduction potential of-0.76V (relative to a reversible hydrogen electrode), and is beneficial to constructing a high-voltage platform battery. The zinc ion secondary battery developed based on the water system electrolyte has the advantages of high energy density, safety, low cost and the like, and is expected to become the development direction of future large-scale energy storage devices. Since the valence state change of host material element ions and electron transfer caused by the deintercalation of zinc ions in the positive electrode material determine the capacity of the battery, the construction of the high-performance positive electrode material is particularly important for obtaining a high-efficiency battery system.
Carbon-based materials have become widely used electrode materials due to their characteristics of good conductivity, durability, environmental friendliness, low cost, and the like. However, most of the commercial carbon-based electrodes have poor cycle performance and low specific capacity, which greatly limits the development of high-performance batteries. Therefore, development of a new carbon-based cathode material to improve the utilization rate of ions as well as specific capacity and cycle performance is urgently needed.
Disclosure of Invention
In view of the above, the invention aims to overcome the defects of the prior art, and provides a preparation method of a vanadium dioxide graphene composite positive electrode material capable of reversibly storing zinc ions by using a heterogeneous interface, wherein the preparation method is simple to operate, the raw materials are cheap and easy to obtain, and the obtained material shows good electrochemical performance when being used as a positive electrode active material of a zinc ion battery, and can be used for solving the problems of poor conductivity, low specific capacity and the like of a commercial positive electrode material.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of a self-supporting vanadium graphene interface zinc storage material comprises the following steps: mixing graphene, vanadium sol and n-propanol, obtaining a vanadium dioxide graphene composite material by adopting a hydrothermal synthesis method, uniformly mixing the vanadium dioxide graphene composite material and the carbon nano tube, crushing, and performing suction filtration to obtain the self-supporting vanadium graphene interface zinc storage material.
Further, the step of mixing graphene, vanadium sol and n-propanol, and obtaining the vanadium dioxide graphene composite material by adopting a hydrothermal synthesis method comprises the following steps:
and mixing the graphene and the vanadium sol, adding the mixture into an n-propanol solution to obtain a mixed solution A, carrying out ultrasonic treatment on the mixed solution A for a first time, carrying out hydrothermal treatment for a second time, washing and drying the obtained precipitate to obtain the vanadium dioxide graphene composite material.
Further, the hydrothermal heating temperature is in the range of 170 ℃ to 190 ℃, and the second time period is in the range of 11 hours to 13 hours.
Further, in the mixed solution A, the content of the graphene is in a range of 0.76mg/mL to 1.29mg/mL, and the content of the vanadium sol is in a range of 4.49mg/mL to 8.5 mg/mL.
Further, uniformly mixing, crushing and filtering the vanadium dioxide graphene composite material and the carbon nano tube to obtain the self-supporting vanadium graphene interface zinc storage material comprises:
mixing the vanadium dioxide graphene composite material and the carbon nano tube, adding the mixture into deionized water, wherein the mass ratio of the addition amount of the carbon nano tube to the total mass is 28-32%, carrying out ultrasonic crushing for a third time, and carrying out suction filtration until the loading amount reaches 1.9mg/cm2To 2.5mg/cm2And obtaining the self-supporting vanadium graphene interface zinc storage material within the range.
Further, the graphene is reduced graphene oxide.
Further, the preparation method of the reduced graphene oxide comprises the following steps:
adding graphite powder into concentrated sulfuric acid, stirring at room temperature for a fourth time, heating in a water bath, adding sodium nitrate, and stirring until the sodium nitrate is completely dissolved to obtain a mixed solution B;
adding potassium permanganate into the mixed solution B, stirring, adding distilled water, and stirring to obtain a graphene oxide solution;
stopping heating in a water bath, and adding distilled water and hydrogen peroxide into the graphene oxide solution to obtain a mixed solution C;
and adding a hydrochloric acid solution into the mixed solution C for washing, adding distilled water for washing to be neutral after washing, dispersing the precipitate in the distilled water, performing ultrasonic treatment, removing the precipitate, and taking supernatant as the solution of the reduced graphene oxide.
Further, the preparation method of the vanadium sol comprises the following steps:
and heating vanadium pentoxide for a fifth time to obtain a melt, adding the melt into distilled water, stirring, cooling to room temperature, and filtering to obtain the vanadium sol.
The invention also aims to provide a self-supporting vanadium-series graphene interface zinc storage material, which is prepared by the preparation method of the self-supporting vanadium-series graphene interface zinc storage material.
Another object of the present invention is to provide an application of the self-supporting vanadium-based graphene interfacial zinc storage material as described above, wherein the self-supporting vanadium-based graphene interfacial zinc storage material is used for a positive electrode active material of a zinc ion battery.
Compared with the prior art, the self-supporting vanadium graphene interface zinc storage material and the preparation method and application thereof provided by the invention have the following advantages:
according to the invention, a hydrothermal method is combined with suction filtration, vanadium dioxide sub-nanoclusters and graphene are compounded, and the vanadium dioxide sub-nanoclusters and the graphene surface form chemical bond connection to form a self-supporting vanadium graphene interface zinc storage material which can be reversibly embedded into a zinc ion heterogeneous interface. The prepared self-supporting vanadium graphene interface zinc storage material is used as a zinc ion battery anode active material, shows good electrochemical performance, excellent rate capability, high specific capacity and high cycle stability, can be used for solving the problems of poor conductivity, low specific capacity and the like of the zinc ion battery anode material, and has the capacity of 100 mA.g-1The self-supporting vanadium graphene interface zinc storage material has a super-theoretical reversible charge-discharge specific capacity (443 mAh. the material has a high specific charge-discharge capacityg-1). In addition, the preparation process and the preparation process of the method are simple to operate, the raw materials are cheap and easy to obtain, and the energy consumption is low, so that the flexible self-supporting vanadium graphene interface zinc storage material without the adhesive and independent can be produced in a large scale.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, a brief description will be given below to the drawings required for the description of the embodiments or the prior art, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without inventive exercise.
Fig. 1 is a flow chart of a preparation method of a self-supporting vanadium-based graphene interface zinc storage material according to an embodiment of the invention;
FIG. 2 is a flow chart of the preparation of a reduced graphene oxide material according to an embodiment of the present invention;
fig. 3 is an XRD pattern of the self-supporting vanadium-based graphene interfacial zinc storage material prepared in example 1 of the present invention;
FIG. 4 is an AC-STEM diagram of the cross section of the self-supporting vanadium-based graphene interface zinc storage material prepared in example 1 of the present invention;
FIG. 5 is an XPS chart of a self-supporting vanadium-based graphene interface zinc storage material prepared in example 1 of the present invention and a comparison thereof;
fig. 6 is a Raman chart of the self-supporting vanadium-based graphene interface zinc storage material prepared in example 1 of the present invention and a comparison thereof;
fig. 7 is an in-situ Raman chart of a self-supporting vanadium-based graphene interface zinc storage material prepared in example 1 of the present invention;
FIG. 8 is a cycle chart of the preparation of the self-supporting vanadium-based graphene interface zinc storage material according to example 1 of the present invention and a comparison thereof;
fig. 9 is a magnification view of the self-supporting vanadium-based graphene interface zinc storage material prepared in example 1 of the present invention and a comparison thereof.
Detailed Description
The principles and features of this invention are described below in conjunction with specific embodiments, the examples given are intended to illustrate the invention and are not intended to limit the scope of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict. The terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. The terms "comprising," "including," "containing," and "having" are intended to be inclusive, i.e., that additional steps and other ingredients may be added without affecting the result.
The invention provides a preparation method of a self-supporting vanadium graphene interface zinc storage material,
as shown in fig. 1, the method includes the following steps:
step S1, mixing the graphene, the vanadium sol and the n-propanol, and obtaining the vanadium dioxide graphene composite material by adopting a hydrothermal synthesis method;
and S2, uniformly mixing the vanadium dioxide graphene composite material with the carbon nano tube, crushing, and performing suction filtration to obtain the self-supporting vanadium graphene interface zinc storage material.
According to the preparation method of the self-supporting vanadium-based graphene interface zinc storage material, a hydrothermal method is combined with suction filtration, vanadium dioxide sub-nanoclusters and graphene are compounded, chemical bonds are formed between the vanadium dioxide sub-nanoclusters and the surface of the graphene, and the self-supporting vanadium-based graphene interface zinc storage material with a heterogeneous interface capable of being reversibly embedded with zinc ions is formed. The prepared self-supporting vanadium graphene interface zinc storage material is used as a zinc ion battery anode active material, shows good electrochemical performance, excellent rate capability, high specific capacity and high cycle stability, can be used for solving the problems of poor conductivity, low specific capacity and the like of the zinc ion battery anode material, and has the capacity of 100 mA.g-1The self-supporting vanadium-series graphene interface zinc storage material has super-theoretical reversible charge-discharge specific capacity (443mAh g)-1). In addition, the preparation process and the preparation process of the method are simple to operate, and the raw materials are cheapThe price is easy to obtain, the energy consumption is low, and the flexible self-supporting vanadium graphene interface zinc storage material without the adhesive and independent can be produced in a large scale.
The independent self-supporting carbon-based material has the characteristics of light weight, good flexibility and high conductivity, and can be used for preparing wearable devices or flexible electrodes. The graphene has good mechanical strength and electrical conductivity, and is beneficial to preparing flexible energy storage materials. Meanwhile, as a self-supporting material, the application of the self-supporting vanadium graphene interface zinc storage material greatly optimizes the existing process flow, and omits the traditional process of adding acetylene black to enhance conductivity and adding a binder. The research and development of the graphene-based electrode material have very important significance for accelerating the development of the new energy battery industry and enhancing the environmental friendliness of the battery industry, and the graphene-based electrode material also becomes a research hotspot of the secondary battery anode material due to the characteristics of stable structure and excellent performance.
Specifically, the step of mixing graphene, vanadium sol and n-propanol, and obtaining the vanadium dioxide graphene composite material by adopting a hydrothermal synthesis method comprises the following steps: and mixing the graphene and the vanadium sol, adding the mixture into an n-propanol solution to obtain a mixed solution A, carrying out ultrasonic treatment on the mixed solution A for a first time, carrying out hydrothermal treatment for a second time, washing and drying the obtained precipitate to obtain the vanadium dioxide graphene composite material.
In the hydrothermal synthesis process, the heating temperature of the hydrothermal process is in the range of 175-185 ℃, and preferably 180 ℃; the second period of time is in the range of 11 hours to 13 hours, preferably 12 hours.
Specifically, in the mixed solution a, the content of the graphene is in a range from 0.76mg/mL to 1.29mg/mL, preferably 1.05mg/mL, that is, 15mL of the mixed solution is added with 15.75mg of graphene; the content of the vanadium sol is 4.49mg/mL to 8.5mg/mL, preferably 6.184mg/mL, namely 15mL of the mixed solution, and 92.76mg of the vanadium sol is added.
In particular, the first period of time is in the range of 25 minutes to 35 minutes, preferably 30 minutes; and washing the obtained precipitate by using deionized water, washing the precipitate for 2 to 5 times, preferably 3 times, and drying to obtain the vanadium dioxide graphene composite material.
Further, uniformly mixing, crushing and filtering the vanadium dioxide graphene composite material and the carbon nano tube to obtain the self-supporting vanadium graphene interface zinc storage material comprises: mixing the vanadium dioxide graphene composite material and the carbon nano tube, adding the mixture into deionized water, wherein the mass ratio of the addition amount of the carbon nano tube to the total mass after the addition is within the range of 28-32%, preferably 30%, carrying out ultrasonic crushing for a third time, and carrying out suction filtration until the loading amount reaches 1.9mg/cm2To 2.5mg/cm2In the range, 2.27mg/cm is preferable2And obtaining the self-supporting vanadium graphene interface zinc storage material.
In particular, the third period of time is in the range of 13 minutes to 17 minutes, preferably 15 minutes.
Specifically, the graphene is reduced graphene oxide, and the reduced graphene oxide is prepared by a Hummers method. The Hummers method is a preparation method of reduced graphene oxide, and adopts potassium permanganate in concentrated sulfuric acid and graphite powder to make oxidation reaction so as to obtain brown graphite flake whose edge possesses derivative carboxylic group and plane is mainly phenol hydroxyl group and epoxy group, said graphite flake layer can be undergone the process of ultrasonic or high-shear intensive stirring and stripped into graphene oxide, and can be formed into stable light brown single-layer graphene oxide suspension in water.
Specifically, this embodiment provides a method for preparing reduced graphene oxide, and as shown in fig. 2, the preparation of the reduced graphene oxide by the Hummers method includes the following steps:
step M1, adding graphite powder into concentrated sulfuric acid, stirring at room temperature for a fourth time, heating in a water bath, adding sodium nitrate, and stirring until the sodium nitrate is completely dissolved to obtain a mixed solution B;
step M2, adding potassium permanganate into the mixed solution B, stirring, adding distilled water, and stirring to obtain a graphene oxide solution;
m3, stopping heating in the water bath, and adding distilled water and hydrogen peroxide into the graphene oxide solution to obtain a mixed solution C;
and M4, adding a hydrochloric acid solution into the mixed solution C for washing, adding distilled water after washing to be neutral, dispersing the precipitate in the distilled water, performing ultrasonic treatment to remove the precipitate, and taking supernatant as the solution of the reduced graphene oxide.
Specifically, in the step M1, the average particle size of the graphite powder is about 300 meshes, and the liquid-solid ratio of the concentrated sulfuric acid to the graphite powder is in the range of 22mL/g to 24mL/g, preferably 23mL/g, that is, 1g of graphite powder is dispersed in 23mL of concentrated sulfuric acid. The fourth period of time is in the range of 23 hours to 25 hours, preferably 24 hours. The temperature at which the water bath is heated is in the range 38 ℃ to 42 ℃, preferably 40 ℃. The mass ratio of the added amount of the sodium nitrate to the graphite powder is in the range of 0.09 to 0.11, preferably 0.1, for example 100mg of sodium nitrate is mixed with 1g of graphite powder.
In the step M2, the mass ratio of the addition amount of the potassium permanganate to the graphite powder is in the range of 0.45 to 0.55, preferably 0.5, for example, 500mg of potassium permanganate is mixed with 1g of graphite powder. The stirring time before adding the distilled water is in the range of 25 minutes to 35 minutes, preferably 30 minutes; the stirring time after the addition of distilled water is 12 to 18 minutes, preferably 15 minutes. The ratio of the amount of the added distilled water to the volume of the concentrated sulfuric acid is in the range of 1.7 to 2.3, preferably 2, such as 46mL of distilled water added to 23mL of concentrated sulfuric acid.
In the step M3, the volume ratio of the added amount of the distilled water to the concentrated sulfuric acid is in the range of 6 to 6.5, preferably 6.09, that is, 140mL of distilled water is added to 23mL of concentrated sulfuric acid. The volume ratio of the added hydrogen peroxide to the concentrated sulfuric acid is in the range of 8/23-12/23, preferably 10/23, namely, 23mL of concentrated sulfuric acid is added with 10mL of hydrogen peroxide.
In the step M4, the hydrochloric acid solution has a concentration of 5%, and the solution is washed with a 5% hydrochloric acid solution for 2 times, and the obtained precipitate is put into distilled water and subjected to ultrasonic treatment for 50 to 70 minutes, preferably 60 minutes. And centrifuging the solution after ultrasonic treatment, and collecting supernatant to obtain the reduced graphene oxide solution.
Specifically, this embodiment also provides a method for preparing a vanadium sol, where the method for preparing a vanadium sol includes:
and heating vanadium pentoxide for a fifth time to obtain a melt, adding the melt into distilled water, stirring, cooling to room temperature, and filtering to obtain the vanadium sol.
Specifically, the vanadium pentoxide is heated at a temperature in the range of 750 ℃ to 850 ℃ for 15 minutes to 25 minutes, preferably 800 ℃ for 20 minutes. And adding the vanadium pentoxide into distilled water, wherein the mass-volume ratio of the vanadium pentoxide to the distilled water is about 0.04 g/mL.
The embodiment of the invention also provides a self-supporting vanadium-series graphene interface zinc storage material, which is prepared by the preparation method of the self-supporting vanadium-series graphene interface zinc storage material.
Specifically, the self-supporting vanadium graphene interface zinc storage material is used for preparing a zinc ion battery positive electrode active material.
On the basis of the above embodiment, the following specific examples of the preparation method of the self-supporting vanadium-based graphene interface zinc storage material are provided in the present invention.
Example 1:
a preparation method of a self-supporting vanadium graphene interface zinc storage material comprises the following steps:
1) dissolving 1g of 300-mesh graphite powder in 23mL of concentrated sulfuric acid, stirring for 24h at room temperature, adding 100mg of sodium nitrate under the condition of 40 ℃ water bath, and stirring for 5 minutes to completely dissolve the sodium nitrate;
2) weighing 500mg of potassium permanganate, slowly adding the potassium permanganate into the solution, stirring for 30 minutes, slowly adding 46mL of distilled water into the solution, and stirring for 15 minutes to obtain a graphene oxide solution;
3) stopping heating in the water bath, and adding 140mL of distilled water and 10mL of hydrogen peroxide into the solution to obtain a reduced graphene oxide solution;
4) adding 67.5mL of concentrated hydrochloric acid into 432.5mL of deionized water for dilution to obtain a 5% hydrochloric acid solution, washing the graphene oxide solution for 2 times by using the hydrochloric acid solution, then washing the graphene oxide solution to be neutral by using distilled water, dispersing the obtained precipitate in 100mL of distilled water, and carrying out ultrasonic treatment for 60 minutes;
5) centrifuging the solution twice to obtain supernatant, namely the reduced graphene oxide solution
6) Weighing 20g of vanadium pentoxide, heating at 800 ℃ for 20 minutes, adding the obtained melt into 500mL of distilled water, stirring, cooling to room temperature, and filtering to obtain vanadium sol;
7) mixing 92.76mg of vanadium sol and 15.75mg of reduced graphene oxide, adding n-propanol until the total volume is 15mL, carrying out ultrasonic treatment on the obtained liquid for 30 minutes, carrying out hydrothermal treatment at 180 ℃ for 12 hours, washing the obtained precipitate with deionized water for 3 times, and airing to obtain a vanadium dioxide graphene composite material;
8) weighing a multi-walled carbon nanotube with the total mass ratio of 30%, mixing the multi-walled carbon nanotube with a vanadium dioxide graphene composite material, dispersing the multi-walled carbon nanotube and the vanadium dioxide graphene composite material into ionized water, carrying out ultrasonic crushing treatment on cells for 15 minutes, and carrying out suction filtration to obtain the load capacity of about 2.27mg/cm2The self-supporting vanadium graphene interface zinc storage material.
Taking the product self-supporting vanadium-based graphene interface zinc storage material prepared in this embodiment as an example, as determined by an X-ray diffractometer, as shown in fig. 3, an X-ray diffraction (XRD) pattern of the self-supporting vanadium-based graphene interface zinc storage material shows that a vanadium dioxide crystal phase is vanadium dioxide (B), and at about 25.5 ° 2 θ, the peak intensity is significantly enhanced, which indicates that the vanadium dioxide is arranged along the 110 crystal plane orientation.
As shown in fig. 4, the dark color sheet is a graphene reduction oxide sheet layer, the bright region is a vanadium dioxide sub-nanocluster, the distance between the graphene reduction oxide (002) surface layers is about 0.336nm, the cluster thickness is about 1.26nm, and the sub-nanocluster is tightly attached to the graphene surface. As shown in fig. 5, XPS test was performed on the self-supporting vanadium-based graphene interface zinc storage material, and compared with the comparative sample, the self-supporting vanadium-based graphene interface zinc storage material is characterized in that a large number of C — O bonds are additionally generated. As shown in fig. 6, Raman test was performed on the self-supporting vanadium-based graphene interface zinc storage material, and the comparison sample of the self-supporting vanadium-based graphene interface zinc storage material is characterized in that O atoms in vanadium dioxide and C atoms in graphene generate V-O-C bonds to connect interfaces. The self-supporting vanadium graphene interface zinc storage material prepared by the invention is used for the positive electrode active material of the zinc ion battery, and compared with the common preparation method of the zinc ion battery, the preparation method of the zinc ion battery omits the addition of adhesiveA step of preparing a binding agent and a conductive agent, namely selecting a self-supporting vanadium graphene interface zinc storage material as a positive electrode of a zinc ion battery, selecting 3M Zn (CF) by taking metal zinc as a negative electrode3SO3)2And (3) assembling the button cell by using the electrolyte, GF/A glass fiber as a diaphragm and CR2016 type stainless steel as a cell shell. In the data shown in fig. 7, the battery is charged and discharged circularly under the in-situ Raman test condition, and chemical bonds at the interface are reversibly formed and broken, so that the interface reversible zinc storage mechanism of the self-supporting vanadium-series graphene interface zinc storage material is verified. The data shown in FIG. 8 shows that the cell was at 100mA g-1The lower cycle charge and discharge showed 443mAh g-1Initial over theoretical capacity and superior cycle stability.
The battery rate performance in the data shown in FIG. 9 is good and at 100Ag-1The high specific capacity of 174mAh & g < -1 > is shown under the high current density, which indicates that the zinc ion conduction and electronic conduction performance of the self-supporting vanadium graphene interface zinc storage material are excellent, and the good conductivity of the material is shown. The test result shows that the self-supporting vanadium graphene interface zinc storage material has excellent electrochemical performance and is a high-performance zinc ion battery positive electrode material.
Example 2:
1) dissolving 1g of 300-mesh graphite powder in 22mL of concentrated sulfuric acid, stirring for 23h at room temperature, adding 90mg of sodium nitrate under the condition of 38 ℃ water bath, and stirring for 5 minutes to completely dissolve the sodium nitrate;
2) weighing 450mg of potassium permanganate, slowly adding the potassium permanganate into the solution, stirring the solution for 25 minutes, slowly adding 37.4mL of distilled water into the solution, and stirring the solution for 12 minutes to obtain a graphene oxide solution;
3) stopping heating in the water bath, and adding 132mL of distilled water and 7.7mL of hydrogen peroxide into the solution to obtain a reduced graphene oxide solution;
4) adding 67.5mL of concentrated hydrochloric acid into 432.5mL of deionized water for dilution to obtain a 5% hydrochloric acid solution, washing the graphene oxide solution for 2 times by using the hydrochloric acid solution, then washing the graphene oxide solution to be neutral by using distilled water, dispersing the obtained precipitate in 100mL of distilled water, and carrying out ultrasonic treatment for 50 minutes;
5) centrifuging the solution twice to obtain supernatant, namely the reduced graphene oxide solution;
6) weighing 20g of vanadium pentoxide, heating at 750 ℃ for 25 minutes, adding the obtained melt into 500mL of distilled water, stirring, cooling to room temperature, and filtering to obtain vanadium sol;
7) mixing 67.35mg of vanadium sol and 11.4mg of reduced graphene oxide, adding n-propanol to the total volume of 15mL, carrying out ultrasonic treatment on the obtained liquid for 25 minutes, carrying out hydrothermal treatment at 175 ℃ for 13 hours, washing the obtained precipitate with deionized water for 2 times, and airing to obtain a vanadium dioxide graphene composite material;
8) weighing multi-walled carbon nanotubes with the total mass percentage of 28%, mixing and dispersing the multi-walled carbon nanotubes and the vanadium dioxide graphene composite material into ionized water, carrying out ultrasonic crushing treatment on cells for 13 minutes, and carrying out suction filtration to obtain the load capacity of about 1.9mg/cm2The self-supporting vanadium graphene interface zinc storage material.
Taking the self-supporting vanadium-based graphene interface zinc storage material obtained in the embodiment as an example, the zinc storage material is prepared at 100mA · g-1The first discharge specific capacity is about 370mAh/g under the current density.
Example 3:
1) dissolving 1g of 300-mesh graphite powder in 24mL of concentrated sulfuric acid, stirring for 25h at room temperature, adding 110mg of sodium nitrate under the condition of 42 ℃ water bath, and stirring for 5 minutes to completely dissolve the sodium nitrate;
2) weighing 550mg of potassium permanganate, slowly adding the potassium permanganate into the solution, stirring for 35 minutes, slowly adding 55.2mL of distilled water into the solution, and stirring for 18 minutes to obtain a graphene oxide solution;
3) stopping heating in the water bath, and adding 156mL of distilled water and 12.5mL of hydrogen peroxide into the solution to obtain a reduced graphene oxide solution;
4) adding 67.5mL of concentrated hydrochloric acid into 432.5mL of deionized water for dilution to obtain a 5% hydrochloric acid solution, washing the graphene oxide solution for 2 times by using the hydrochloric acid solution, then washing the graphene oxide solution to be neutral by using distilled water, dispersing the obtained precipitate in 100mL of distilled water, and carrying out ultrasonic treatment for 70 minutes;
5) centrifuging the solution twice to obtain supernatant, namely the reduced graphene oxide solution;
6) weighing 20g of vanadium pentoxide, heating at 850 ℃ for 15 minutes, adding the obtained melt into 500mL of distilled water, stirring, cooling to room temperature, and filtering to obtain vanadium sol;
7) mixing 127.5mg of vanadium sol and 19.35mg of reduced graphene oxide, adding n-propanol until the total volume is 15mL, carrying out ultrasonic treatment on the obtained liquid for 35 minutes, carrying out hydrothermal treatment at 185 ℃ for 11 hours, washing the obtained precipitate with deionized water for 5 times, and airing to obtain a vanadium dioxide graphene composite material;
8) weighing a multi-walled carbon nanotube accounting for 32 percent of the total mass, mixing the multi-walled carbon nanotube with a vanadium dioxide graphene composite material, dispersing the multi-walled carbon nanotube and the vanadium dioxide graphene composite material into ionized water, carrying out ultrasonic crushing treatment on cells for 17 minutes, and carrying out suction filtration to obtain the load capacity of about 2.3mg/cm2The self-supporting vanadium graphene interface zinc storage material.
Taking the self-supporting vanadium-based graphene interface zinc storage material obtained in the embodiment as an example, the zinc storage material is prepared at 100mA · g-1The first discharge specific capacity is about 341mAh/g under the current density.
Example 4:
1) dissolving 1g of 300-mesh graphite powder in 23mL of concentrated sulfuric acid, stirring for 24h at room temperature, adding 100mg of sodium nitrate under the condition of 40 ℃ water bath, and stirring for 5 minutes to completely dissolve the sodium nitrate;
2) weighing 500mg of potassium permanganate, slowly adding the potassium permanganate into the solution, stirring for 30 minutes, slowly adding 46mL of distilled water into the solution, and stirring for 15 minutes to obtain a graphene oxide solution;
3) stopping heating in the water bath, and adding 140mL of distilled water and 10mL of hydrogen peroxide into the solution to obtain a reduced graphene oxide solution;
4) adding 67.5mL of concentrated hydrochloric acid into 432.5mL of deionized water for dilution to obtain a 5% hydrochloric acid solution, washing the graphene oxide solution for 2 times by using the hydrochloric acid solution, then washing the graphene oxide solution to be neutral by using distilled water, dispersing the obtained precipitate in 100mL of distilled water, and carrying out ultrasonic treatment for 60 minutes;
5) centrifuging the solution twice to obtain supernatant, namely the reduced graphene oxide solution
6) Weighing 20g of vanadium pentoxide, heating at 800 ℃ for 20 minutes, adding the obtained melt into 500mL of distilled water, stirring, cooling to room temperature, and filtering to obtain vanadium sol;
7) mixing 127.5 vanadium sol and 15.75mg of reduced graphene oxide, adding n-propanol until the total volume is 15mL, carrying out ultrasonic treatment on the obtained liquid for 30 minutes, carrying out hydrothermal treatment at 180 ℃ for 12 hours, washing the obtained precipitate with deionized water for 3 times, and airing to obtain a vanadium dioxide graphene composite material;
8) weighing a multi-walled carbon nanotube with the total mass ratio of 30%, mixing the multi-walled carbon nanotube with a vanadium dioxide graphene composite material, dispersing the multi-walled carbon nanotube and the vanadium dioxide graphene composite material into ionized water, carrying out ultrasonic crushing treatment on cells for 15 minutes, and carrying out suction filtration to obtain the load capacity of about 1.9mg/cm2The self-supporting vanadium graphene interface zinc storage material.
Taking the self-supporting vanadium-based graphene interface zinc storage material obtained in the embodiment as an example, the zinc storage material is prepared at 100mA · g-1Under the current density, the first discharge specific capacity can reach 367 mAh/g.
Example 5:
1) dissolving 1g of 300-mesh graphite powder in 23mL of concentrated sulfuric acid, stirring for 24h at room temperature, adding 100mg of sodium nitrate under the condition of 40 ℃ water bath, and stirring for 5 minutes to completely dissolve the sodium nitrate;
2) weighing 500mg of potassium permanganate, slowly adding the potassium permanganate into the solution, stirring for 30 minutes, slowly adding 46mL of distilled water into the solution, and stirring for 15 minutes to obtain a graphene oxide solution;
3) stopping heating in the water bath, and adding 140mL of distilled water and 10mL of hydrogen peroxide into the solution to obtain a reduced graphene oxide solution;
4) adding 67.5mL of concentrated hydrochloric acid into 432.5mL of deionized water for dilution to obtain a 5% hydrochloric acid solution, washing the graphene oxide solution for 2 times by using the hydrochloric acid solution, then washing the graphene oxide solution to be neutral by using distilled water, dispersing the obtained precipitate in 100mL of distilled water, and carrying out ultrasonic treatment for 60 minutes;
5) centrifuging the solution twice to obtain supernatant, namely the reduced graphene oxide solution
6) Weighing 20g of vanadium pentoxide, heating at 800 ℃ for 20 minutes, adding the obtained melt into 500mL of distilled water, stirring, cooling to room temperature, and filtering to obtain vanadium sol;
7) mixing 92.75mg of vanadium sol and 11.4mg of reduced graphene oxide, adding n-propanol until the total volume is 15mL, carrying out ultrasonic treatment on the obtained liquid for 30 minutes, carrying out hydrothermal treatment at 180 ℃ for 12 hours, washing the obtained precipitate with deionized water for 3 times, and airing to obtain a vanadium dioxide graphene composite material;
8) weighing a multi-walled carbon nanotube with the total mass ratio of 30%, mixing the multi-walled carbon nanotube with a vanadium dioxide graphene composite material, dispersing the multi-walled carbon nanotube and the vanadium dioxide graphene composite material into ionized water, carrying out ultrasonic crushing treatment on cells for 15 minutes, and carrying out suction filtration to obtain the load capacity of about 2.5mg/cm2The self-supporting vanadium graphene interface zinc storage material.
Taking the self-supporting vanadium-based graphene interface zinc storage material obtained in the embodiment as an example, the zinc storage material is prepared at 100mA · g-1The first discharge specific capacity is about 374mAh/g under the current density.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A preparation method of a self-supporting vanadium graphene interface zinc storage material is characterized by comprising the following steps: mixing graphene, vanadium sol and n-propanol, obtaining a vanadium dioxide graphene composite material by adopting a hydrothermal synthesis method, uniformly mixing the vanadium dioxide graphene composite material with a carbon nano tube, crushing, and performing suction filtration to obtain the self-supporting vanadium graphene interface zinc storage material.
2. The method for preparing the self-supporting vanadium-based graphene interface zinc storage material according to claim 1, wherein the step of mixing graphene, vanadium sol and n-propanol and obtaining the vanadium dioxide graphene composite material by a hydrothermal synthesis method comprises the following steps:
and mixing the graphene and the vanadium sol, adding the mixture into an n-propanol solution to obtain a mixed solution A, carrying out ultrasonic treatment on the mixed solution A for a first time, carrying out hydrothermal treatment for a second time, washing and drying the obtained precipitate to obtain the vanadium dioxide graphene composite material.
3. The method for preparing the self-supporting vanadium-based graphene interfacial zinc storage material according to claim 2, wherein the hydrothermal heating temperature is in a range of 170 ℃ to 190 ℃, and the second time period is in a range of 11 hours to 13 hours.
4. The preparation method of the self-supporting vanadium-based graphene interfacial zinc storage material according to claim 2, wherein in the mixed solution A, the content of graphene is in a range of 0.76mg/mL to 1.29mg/mL, and the content of vanadium sol is in a range of 4.49mg/mL to 8.5 mg/mL.
5. The preparation method of the self-supporting vanadium-series graphene interface zinc storage material according to claim 1, wherein the step of uniformly mixing the vanadium dioxide graphene composite material with the carbon nanotube, crushing, and performing suction filtration to obtain the self-supporting vanadium-series graphene interface zinc storage material comprises the following steps:
mixing the vanadium dioxide graphene composite material and the carbon nano tube, adding the mixture into deionized water, wherein the mass ratio of the addition amount of the carbon nano tube to the total mass is 28-32%, carrying out ultrasonic crushing for a third time, and carrying out suction filtration until the loading amount reaches 1.9mg/cm2To 2.5mg/cm2And obtaining the self-supporting vanadium graphene interface zinc storage material within the range.
6. The method for preparing the self-supporting vanadium-based graphene interface zinc storage material according to any one of claims 1 to 5, wherein the graphene is reduced graphene oxide.
7. The method for preparing the self-supporting vanadium-based graphene interface zinc storage material according to claim 6, wherein the method for preparing the reduced graphene oxide comprises the following steps:
adding graphite powder into concentrated sulfuric acid, stirring at room temperature for a fourth time, heating in a water bath, adding sodium nitrate, and stirring until the sodium nitrate is completely dissolved to obtain a mixed solution B;
adding potassium permanganate into the mixed solution B, stirring, adding distilled water, and stirring to obtain a graphene oxide solution;
stopping heating in a water bath, and adding distilled water and hydrogen peroxide into the graphene oxide solution to obtain a mixed solution C;
and adding a hydrochloric acid solution into the mixed solution C for washing, adding distilled water for washing to be neutral after washing, dispersing the precipitate in the distilled water, performing ultrasonic treatment, removing the precipitate, and taking supernatant as the solution of the reduced graphene oxide.
8. The preparation method of the self-supporting vanadium-based graphene interfacial zinc storage material according to any one of claims 1 to 5, wherein the preparation method of the vanadium sol comprises the following steps:
and heating vanadium pentoxide for a fifth time to obtain a melt, adding the melt into distilled water, stirring, cooling to room temperature, and filtering to obtain the vanadium sol.
9. A self-supporting vanadium-series graphene interface zinc storage material is characterized by being prepared by the preparation method of the self-supporting vanadium-series graphene interface zinc storage material according to any one of claims 1 to 8.
10. The use of the self-supporting vanadium-based graphene interfacial zinc storage material according to claim 9, wherein the self-supporting vanadium-based graphene interfacial zinc storage material is used for preparing a zinc ion battery positive electrode active material.
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